US20190330565A1 - Detergent compositions containing copolymer - Google Patents

Detergent compositions containing copolymer Download PDF

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Publication number
US20190330565A1
US20190330565A1 US16/462,915 US201716462915A US2019330565A1 US 20190330565 A1 US20190330565 A1 US 20190330565A1 US 201716462915 A US201716462915 A US 201716462915A US 2019330565 A1 US2019330565 A1 US 2019330565A1
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Prior art keywords
laundry detergent
component
detergent composition
structural units
structural unit
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Kevin James MUTCH
Natascha Schelero
Dorothee GABEL
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Clariant International Ltd
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Clariant International Ltd
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Assigned to CLARIANT INTERNATIONAL LTD reassignment CLARIANT INTERNATIONAL LTD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHELERO, Natascha, MUTCH, Kevin, GABEL, Dorothee
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0036Soil deposition preventing compositions; Antiredeposition agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to laundry detergent compositions comprising copolymers (polymer additives) containing one or more cationic structural units and one or more macromonomeric structural units, and to the use of the laundry detergent compositions or of the copolymers for cleaning textiles, preferably cotton-containing textiles, or for reducing the restaining of textiles, preferably of cotton-containing textiles, on which the laundry detergent compositions or the copolymers have been employed.
  • the copolymers present in the laundry detergent compositions of the invention can thus function as soil release polymers, especially when used on cotton-containing textiles.
  • soil release polymers in laundry detergent compositions is customary. It is assumed that soil release polymers are deposited on the fiber, and alter the surface properties thereof in such a way that soil can be more readily detached from the fiber.
  • What are typically used for predominantly polyester-based textiles are derivatives of polymers of terephthalic acid and polyethylene glycol (e.g. E. P. Gosselink, “Soil Release Agents in Powdered Detergents”, ch. 7 (pp. 205-239) in Surfactant Science Series 71, “Powdered Detergents”).
  • WO 97/42293 describes a laundry detergent formulation comprising water-soluble or water-dispersible polyamines having a functionalized polymer backbone, which imparts soil release properties to cotton.
  • EP 0936224 describes water-soluble or water-dispersible polymers bearing polysaccharide units. One use described is that in laundry detergent compositions.
  • WO 01/88075 discloses the use of anionically modified polysaccharides which, in laundry detergent compositions, assure better detachment of oily or greasy stains on cotton.
  • EP 1972683 describes ampholytic water-soluble polymers which, in laundry detergent composition, protect the fibers from oily or greasy soils.
  • U.S. Pat. No. 7,160,947 describes graft copolymers having soil release properties in laundry detergent compositions. These polymers preferably have 2-dimethylaminoethyl (meth)acrylate side chains, polyethylene oxide (meth)acrylate side chains, and are obtained by means of free-radical polymerization.
  • WO 2015/078736 describes polymers which contain hydrophilic side chains based on polyethylene oxide and 2-dimethylaminoethyl (meth)acrylate and assure improved soil release properties in laundry detergent formulations.
  • WO 2013/060708 uses comb copolymers or block copolymers as graying inhibitors and soil release polymers, including on cotton.
  • the invention therefore provides laundry detergent compositions comprising
  • the laundry detergent compositions of the invention may be in liquid form or in powder form under standard conditions (25° C., 1 atmosphere (1 atm)).
  • the copolymers of component Z1) of the laundry detergent compositions of the invention can easily be prepared synthetically and in water, which is an environmentally friendly solvent.
  • a further advantage of the invention is that the copolymers of component Z1) of the laundry detergent compositions of the invention can be formulated in standard laundry detergent compositions because they are water-soluble. Moreover, they have a high affinity for cotton, but without functioning as a soil magnet. Textiles which are pretreated with the laundry detergent compositions of the invention can be more easily freed of greasy stains.
  • the laundry detergent compositions of the invention or the copolymers of component Z1) present therein protect textiles and especially cotton textiles from soil in an advantageous manner, and lead to a very advantageous cleaning performance.
  • WO 2012/076365 A1 discloses cationic copolymers containing cationic structural units and macromonomeric structural units, and the use thereof as additive for building material systems, especially based on calcium sulfate.
  • WO 2008/049549 A2 describes hydrophobically modified cationic copolymers having at least three different structural units, one structural unit of which has a terminal phenyl group or specifically substituted phenyl group. With the aid of the copolymers, especially in combination with anionic surfactants, even in the case of high salt burdens, it is possible to achieve a considerable improvement in water retention in aqueous building material systems based on hydraulic binders such as cement.
  • WO 2008/141844 A1 describes dispersions comprising inorganic particles, water and at least one water-soluble polymer.
  • the at least one water-soluble polymer has repeat units derived from monomers having at least one quaternary ammonium group, repeat units derived from monomers having at least one carboxyl group, and repeat units derived from polyoxyalkylene group-containing ester monomers having a number-average molecular weight in the range from 3000 g/mol to 10 000 g/mol.
  • the dispersions can especially be used for production of concrete and can be processed over a very long period of time.
  • WO 2008/046652 A1 describes graft polymers obtainable by copolymerization of at least one specific macromonomer and at least one further monomer having a polymerizable ethylenically unsaturated double bond, and the use thereof as dispersants, for example in pigment concentrates.
  • US 2011/0144264 A1 describes the use of substances such as polyethylene glycol (meth)acrylates or poly(ethylene-co-propylene) glycol (meth)acrylates, for example, which, during the process of latex production, can contribute to stabilization through emulsion polymerization of at least one polymerizable monomer.
  • JP 2008-056711 A discloses copolymers which have a number-average molecular weight of 5000 to 1 000 000 and contain structural units which are formed by polymerization of particular cationic monomers, polyoxyalkylene-modified monomers and crosslinkable monomers, and which may additionally contain further structural units which are formed by polymerization of further monomers that can be copolymerized with the aforementioned monomers.
  • the copolymers can be used, for example, as antistats for thermoplastic polymers.
  • the one or more cationic structural units (A) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention is/are the polymerization product of at least one monomer species selected from the group consisting of [2-(acryloyloxy)ethyl]trimethylammonium chloride, [2-(acryloylamino)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methosulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride or methosulfate, [3-(acryloylamino)propyl]trimethylammonium chloride, [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride (DADMAC),
  • DADMAC diallyldimethylammonium chloride
  • the one or more cationic structural units (A) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention more preferably being the polymerization product of at least one monomer species selected from the group consisting of [3-(acryloylamino)propyl]trimethylammonium chloride, [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride, and
  • the one or more cationic structural units (A) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention especially preferably being the polymerization product of at least one monomer species selected from the group consisting of [3-(methacryloylamino)propyl]trimethylammonium chloride and [3-(acryloylamino)propyl]trimethylammonium chloride.
  • the one or more macromonomeric structural units (B) of the formula (III) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention are the polymerization product of at least one monomer species selected from the group consisting of polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether (in which I on molar average is a number from 1 to 6, preferably from 1 to 5 and more preferably from 2 to 5), polyethylene glycol (meth)acrylate and polyethylene glycol-co-polypropylene glycol (meth)acrylate (in which I on molar average is a number from 1 to 6, preferably from 1 to 5 and more preferably from 2 to 5).
  • monomer species selected from the group consisting of polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether (in which I on molar average is a number from 1 to 6, preferably from
  • (meth)acrylate encompasses both the corresponding acrylate compound and the corresponding methacrylate compound.
  • R x is H
  • Z
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain(s)
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain(s) structural units (A) and (B) only as repeat structural units, and no further repeat structural units beyond that.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain(s) the one or more structural units (A) preferably in an amount of 30 to 70 mol % and more preferably in an amount of 40 to 60 mol %, and the one or more structural units (B) preferably in an amount of 70 to 30 mol % and more preferably in an amount of 60 to 40 mol %.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain(s) both one or more macromonomer structural units B-1) and one or more macromonomer structural units B-2, and the molar ratio of (macromonomer structural units B-1):(macromonomer structural units B-2) in these copolymers of component Z1) is preferably from 70:30 to 30:70, more preferably from 60:40 to 40:60 and especially preferably 50:50.
  • the one or more structural units (A) are the polymerization product of at least one monomer species selected from the group consisting of [3-(methacryloylamino)propyl]trimethylammonium chloride and [3-(acryloylamino)propyl]trimethylammonium chloride.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention in addition to the structural units (A) and (B), contain(s) one or more structural units (C) which differ from the structural units (A) and (B), where the one or more copolymers contain preferably 0.1 to 99.8 mol % of the one or more structural units (A), 0.1 to 99.8 mol % of the one or more structural units (B) and 0.1 to 99.8 mol % of the one or more structural units (C),
  • the one or more structural units (C) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention are the polymerization product of at least one monomer species selected from the group consisting of noncationic acrylamides, noncationic methacrylamides and N-vinyl-substituted lactams having 5 to 7 ring atoms.
  • the one or more structural units (C) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention are selected from the group consisting of the polymerization product of at least one N-vinyl-substituted lactam having 5 to 7 ring atoms and the structural units of the formulae (IV) and (V):
  • a preferred polymerization product selected from N-vinyl-substituted lactams having 5 to 7 ring atoms is the polymerization product of N-vinylpyrrolidone.
  • the SO 3 H, PO 3 H 2 , O—PO 3 H 2 and para-substituted C 6 H 4 —SO 3 H groups in the structural units of the formula (V) may also be in salt form, preferably in the form of the NH 4 + , alkali metal or alkaline earth metal salt and more preferably of the NH 4 + salt or Na + salt.
  • R 13 is N(CH 3 ) 2
  • the one or more structural units (C) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention is/are selected from the structural units of the formula (IV).
  • the one or more structural units (C) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention are the polymerization product of at least one monomer species selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N-isopropylacrylamide and N-tert-butylacrylamide, the one or more structural units (C) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention even more preferably being the polymerization product of at least one monomer species selected from the group consisting of N,N-dimethylacrylamide and N-isopropylacrylamide, the one or more structural units (C) of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention even further preferably being the polymerization product
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain(s) structural units (A), (B) and (C) only as repeat structural units, and no further repeat structural units beyond that.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain(s) the one or more structural units (A) preferably in an amount of 15.0 to 65.0 mol % and more preferably in an amount of 20.0 to 60.0 mol %, the one or more structural units (B) preferably in an amount of 15.0 to 45.0 mol % and more preferably in an amount of 20.0 to 40.0 mol %, and the one or more structural units (C) preferably in an amount of 5.0 to 55.0 mol % and more preferably in an amount of 10.0 to 50.0 mol %.
  • the one or more structural units (A) are the polymerization product of at least one monomer species selected from the group consisting of [3-(methacryloylamino)propyl]trimethylammonium chloride and [3-(acryloylamino)propyl]trimethylammonium chloride
  • the one or more structural units (B) are selected from the group consisting of the macromonomer structural units B-1 and the macromonomer structural units B-2
  • the one or more structural units (C) are the polymerization product of at least one monomer species selected from the group consisting of N,N-dimethylacrylamide, N-isopropylacrylamide, 2-acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention in a particularly preferred embodiment of the invention, contain either macromonomer structural units B-1 only or macromonomer structural units B-2 only.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention in another particularly preferred embodiment of the invention, contain both macromonomer structural units B-1 and macromonomer structural units B-2.
  • the molar ratio of (macromonomer structural units B-1):(macromonomer structural units B-2) is preferably from 1:20 to 20:1 and more preferably from 1:15 to 15:1.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention in addition to the structural units (A), (B) and (C), contain(s) one or more structural units (D) which differ from the structural units (A), (B) and (C), where the one or more copolymers contain preferably 0.1 to 99.7 mol % of the one or more structural units (A), 0.1 to 99.7 mol % of the one or more structural units (B), 0.1 to 99.7 mol % of the one or more structural units (C) and 0.1 to 99.7 mol % of the one or more structural units (D), more preferably 12.0 to 50.0 mol % of the one or more structural units (A), 15.0 to 50.0 mol % of the one or more structural units (B), 0.1 to 38.0 mol % of the one or more structural units (C) and 0.1 to 35.0 mol % of the one or more structural units (D), and especially preferably 12.0
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain one or more structural units (D), in a particularly preferred embodiment of the invention, they contain one or more structural units (D) selected from the structural units of the following formula (VIII):
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain one or more structural units (D), these are selected, in an especially preferred embodiment of the invention, from the structural units of the formula (VIII).
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain one or more structural units (D), in a further particularly preferred embodiment of the invention, they contain one or more structural units (D) selected from the structural units of the following formulae (IX) and/or (X):
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain one or more structural units (D), these are selected, in a further especially preferred embodiment of the invention, from the structural units of the formulae (IX) and/or (X).
  • the structural units of the formula (X) may also be in salt form, preferably in the form of the NH 4 + , alkali metal or alkaline earth metal salt and more preferably in the form of the NH 4 + salt or in the form of the Na + salt.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain one or more structural units (D), in a further particularly preferred embodiment of the invention, they contain one or more structural units (D) selected from the structural units of the following formula (VII):
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain one or more structural units (D), these are selected, in a further especially preferred embodiment of the invention, from the structural units of the formula (VII).
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain one or more structural units (D), in a further particularly preferred embodiment of the invention, they contain one or more structural units (D) selected from the structural units of the following formulae (Va), (Vb) and/or (Vc):
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain one or more structural units (D), these are selected, in a further especially preferred embodiment of the invention, from the structural units of the formulae (Va), (Vb) and/or (Vc).
  • the SO 3 H, PO 3 H 2 , O—PO 3 H 2 and para-substituted C 6 H 4 —SO 3 H groups in the structural units of the formula (Vc) may also be in salt form, preferably in the form of the NH 4 + , alkali metal or alkaline earth metal salt and more preferably of the NH 4 + salt or of the Na + salt.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain(s) structural units (A), (B), (C) and (D) only as repeat structural units, and no further repeat structural units beyond that.
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention contain(s) the one or more structural units (A) preferably in an amount of 5.0 to 35.0 mol % and more preferably in an amount of 10.0 to 30.0 mol %, the one or more structural units (B) preferably in an amount of 5.0 to 35.0 mol % and more preferably in an amount of 10.0 to 30.0 mol %, the one or more structural units (C) preferably in an amount of 20.0 to 50.0 mol % and more preferably in an amount of 25.0 to 45.0 mol %, and the one or more structural units (D) preferably in an amount of 10.0 to 40.0 mol % and more preferably in an amount of 15.0 to 35.0 mol %.
  • the one or more structural units (A) preferably in an amount of 5.0 to 35.0 mol % and more preferably in an amount of 10.0 to 30.0 mol %
  • the one or more structural units (B) preferably in an amount of
  • the one or more structural units (A) are the polymerization product of at least one monomer species selected from the group consisting of [3-(methacryloylamino)propyl]trimethylammonium chloride and [3-(acryloylamino)propyl]trimethylammonium chloride
  • the one or more structural units (B) are selected from the group consisting of the macromonomer structural units B-1 and the macromonomer structural units B-2, preferably containing both macromonomer structural units B-1 and macromonomer structural units B-2
  • the one or more structural units (C) are the polymerization product of at least one monomer species selected from the group consisting of N,N-dimethylacrylamide and N-isopropylacrylamide, preferably of N-isopropylacrylamide
  • the one or more structural units (D) are the polymerization product of at least one monomer species selected from the group consisting of acrylic acid, methacrylic acid, the salts of
  • the one or more copolymers of component Z1) of the laundry detergent compositions of the invention preferably contain both macromonomer structural units B-1 and macromonomer structural units B-2.
  • the molar ratio of (macromonomer structural units B-1):(macromonomer structural units B-2) is preferably from 1:20 to 20:1 and more preferably from 1:15 to 15:1.
  • the structural units (A), (B) and, if present, (C) and (D) in the one or more copolymers of component Z1) of the laundry detergent compositions of the invention are in a random, blockwise, alternating or gradient distribution in the copolymer.
  • the weight-average molecular weight M w of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention is from 10 000 to 400 000 g/mol, more preferably from 15 000 to 350 000 g/mol and especially preferably from 50 000 to 330 000 g/mol.
  • the weight-average molecular weight M w of the copolymers of component Z1) of the laundry detergent compositions of the invention can be determined by gel permeation chromatography (GPC), preferably as follows: 10 ⁇ L of the sample are injected into a PSS Novema Max Guard column of the following dimensions: 300 ⁇ 8 mm with a permeability of 1 ⁇ 30 ⁇ and 2 ⁇ 1000 ⁇ and particle size of 10 ⁇ m. Detection is effected via the refractive index at 25° C. The eluent used is 79.7% by volume of 0.1 M NaCl+0.3% by volume of TFA (trifluoroacetic acid)+20.0% by volume of ACN (acetonitrile).
  • GPC gel permeation chromatography
  • Separation is effected at a flow rate of 1 mL/minute.
  • the size is determined by comparison with the elution time of standard samples of poly(2-vinylpyridines) of defined molecular weights in the range from 1110 to 1 060 000 daltons.
  • the Rs1, Rs2, Rs3 and Rs4 radicals are not defined here in detail, but merely for the sake of completeness are specified as radicals bonded to the corresponding carbon atoms “C”.
  • the structural units (A) and (B) that are present in the copolymers of component Z1) and the structural units (C) and (D) that are optionally additionally present in the copolymers of component Z1) are, for example, repeat structural units of this kind.
  • Structural units that originate, for example, from free-radical initiators or from any chain-transfer agents used in the copolymerization are not repeat structural units. Accordingly, repeat structural units are not understood to mean terminal groups, for example.
  • the amounts in mol % that are stated for the structural units (A), (B), (C) and (D) are based on the total amount of the repeat structural units present in the respective copolymers of component Z1).
  • the copolymers of component Z1) of the laundry detergent compositions of the invention can be prepared by methods familiar to those skilled in the art. More preferably, the copolymers of component Z1) can be prepared by free-radical solution polymerization. Standard solvents may preferably be polar solvents such as alcohols or water, and alcohol-water mixtures. The polymerization is initiated by free-radical sources, for example inorganic persulfates, organic azo compounds, peroxides, hydroperoxides, inorganic redox systems, or UV light. In addition, it is possible to use chain-transfer agents that form less reactive free radicals, in order to control the molecular weight of the copolymers.
  • free-radical sources for example inorganic persulfates, organic azo compounds, peroxides, hydroperoxides, inorganic redox systems, or UV light.
  • chain-transfer agents that form less reactive free radicals, in order to control the molecular weight of the copolymers.
  • Chain-transfer agents of this kind are, for example, phenols, thiols, for example sodium 2-mercaptoethanesulfonate, or sodium hypophosphite.
  • the monomers for preparation of the copolymers of component Z1) and, if appropriate, a chain-transfer agent are dissolved in the solvent, oxygen is driven out, then the temperature is increased, and the free-radical initiator is metered in. The copolymerization is then conducted at the desired temperature for the desired period of time.
  • the reaction mixture is then optionally cooled and the copolymer formed is either processed further in solution or worked up; for example, the solution containing the copolymer can be concentrated by partly evaporating off the solvent, optionally under reduced pressure, or the solvent can be removed completely by evaporating it off or else the copolymer can be isolated in some other way, for example by freeze-drying or precipitation.
  • the one or more surfactants of component Z2) of the laundry detergent compositions of the invention are selected from the group consisting of anionic, nonionic, amphoteric and cationic surfactants.
  • the one or more surfactants of component Z2) of the laundry detergent compositions of the invention are selected from the group consisting of fatty alcohol polyglycol ethers, alkyl polyglycosides, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates, glucamides, amine oxides, betaines and quaternary ammonium compounds.
  • anionic surfactants are alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, alkanesulfonates, alkyl ether carboxylic acids, sulfosuccinates, isethionates, taurates, glycinates and/or acylglutamates.
  • the alkyl chains of the surfactants mentioned may be of synthetic or natural origin and consist preferably of 8 to 30, more preferably 8 to 18 and especially preferably 12 to 14 carbon atoms in a linear or branched arrangement.
  • Anionic surfactants that are used in accordance with the invention are preferably aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, n-alkyl ether sulfonates, este
  • alkylbenzenesulfonates fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates, and also [alpha]-sulfo fatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • fatty alcohol sulfates and/or fatty alcohol ether sulfates preference is given to the fatty alcohol sulfates.
  • Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols
  • fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • alkoxylated alcohols generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols.
  • n moles of ethylene oxide and one mole of alcohol give rise to a complex mixture of addition products of different degrees of ethoxylation.
  • a further embodiment of the alkoxylation involves the use of mixtures of alkylene oxides, preferably of the mixture of ethylene oxide and propylene oxide.
  • Preferred fatty alcohol ether sulfates are the sulfates of fatty alcohols having low levels of ethoxylation with 1 to 4 ethylene oxide units (EO), especially 1 to 2 EO, for example 1.3 EO.
  • alkylbenzenesulfonate alkanesulfonate, alkyl ether sulfate or alkyl sulfate.
  • the anionic surfactants are typically used in the form of salts, but also in acid form.
  • the salts are preferably alkali metal salts, alkaline earth metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, especially lithium, sodium, potassium or ammonium salts, more preferably sodium or potassium salts, especially preferably sodium salts.
  • surfactants may be nonionic, amphoteric and/or cationic surfactants, for example betaines, amidobetaines, amine oxides, amidoamine oxides, fatty alcohol polyglycol ethers, alkyl polyglycosides or else quaternary ammonium compounds.
  • nonionic surfactants may, for example, be alkoxylates, such as polyglycol ethers, fatty alcohol polyglycol ethers (fatty alcohol alkoxylates), alkyl phenol polyglycol ethers, end group-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers, and fatty acid polyglycol esters.
  • alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers (fatty alcohol alkoxylates), alkyl phenol polyglycol ethers, end group-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers, and fatty acid polyglycol esters.
  • ethylene oxide-propylene oxide block polymers and fatty acid alkanolamides and fatty acid polyglycol ethers.
  • a further important class of nonionic surfactants that can be used in accordance with the invention is that of the polyol surfactants and here particularly the glycosurfact
  • Suitable fatty alcohol polyglycol ethers are ethylene oxide (EO)- and/or propylene oxide (PO)-alkoxylated, unbranched or branched, saturated or unsaturated C 8 -C 22 alcohols having an alkoxylation level of up to 30, preferably ethoxylated C 10 -C 18 fatty alcohols having an ethoxylation level of less than 30, more preferably 1 to 20, especially preferably 1 to 12 and exceptionally preferably 1 to 8, for example C 12 -C 14 fatty alcohol ethoxylates with 8 EO.
  • EO ethylene oxide
  • PO propylene oxide
  • Alkyl polyglycosides are surfactants that can be obtained by the reaction of sugars and alcohols by the relevant methods of preparative organic chemistry, which results in a mixture of monoalkylated, oligomeric or polymeric sugars according to the manner of preparation.
  • Preferred alkyl polyglycosides are the alkyl polyglucosides, where the alcohol is more preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols having branched or unbranched C 8 - to C 8 a-alkyl chains and the oligomerization level (DP) of the sugars is between 1 and 10, preferably 1 to 6, more preferably 1.1 to 3 and especially preferably 1.1 to 1.7, for example C 8 -C 10 -alkyl-1.5-glucoside (DP of 1.5).
  • the alcohol is more preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols having branched or unbranched C 8 - to C 8 a-alkyl chains and the oligomerization level (DP) of the sugars is between 1 and 10, preferably 1 to 6, more preferably 1.1 to 3 and especially preferably 1.1 to 1.7, for example C 8 -C 10 -alkyl-1.5-glucoside (DP of 1.5).
  • amphosurfactants that are usable in accordance with the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids and biosurfactants.
  • Suitable betaines are the alkyl betaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the amidosulfobetaines, and also the phosphobetaines.
  • betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl Betaine, Apricotam idopropylbetaine, Avocadam idopropylbetaine, Babassuam idopropylbetaine, Behenamidopropylbetaine, Behenylbetaine, Betaine, Canolamidopropylbetaine, Capryl/Capramidopropylbetaine, Carnitine, Cetylbetaine, Cocamidoethylbetaine, Cocamidopropylbetaine, Cocam idopropylhydroxysultaine, Cocobetaine, Cocohydroxysultaine, Coco/Oleamidopropylbetaine, Coco-Sultaine, Decylbetaine, Dihydroxyethyloleylglycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethylstearylglycinate, Dihydroxyethyl Tallow Glylbe
  • the amine oxides suitable in accordance with the invention include alkylamine oxides, especially alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • Suitable amine oxides are the following compounds named according to INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidine Oxide, Dihydroxyethyl C 8 -C 10 Alkoxypropylamine Oxide, Dihydroxyethyl C 9 -C 11 Alkoxypropylamine Oxide, Dihydroxyethyl C 12 -C 15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxy
  • Illustrative alkylamidoalkylamines are the following compounds named according to INCI: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxya
  • Illustrative alkyl-substituted amino acids are the following compounds named according to INCI: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA-Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C 12 -C 15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA-La
  • the laundry detergent compositions of the invention comprise, in addition to the one or more copolymers of component Z1) and the one or more surfactants of component Z2), one or more further substances selected from components Z3), Z4), Z5), Z6) and/or Z7):
  • the complexing agents (INCI Chelating Agents) of component Z3), also called sequestrants, are ingredients able to complex and inactivate metal ions, in order to prevent their adverse effects on the stability or appearance of the compositions, for example cloudiness. It is firstly important to complex the calcium and magnesium ions of water hardness that are incompatible with numerous ingredients. The complexation of the ions of heavy metals such as iron or copper secondly delays the oxidative breakdown of the finished compositions. Moreover, the complexing agents promote detergent action.
  • Suitable examples are the following complexing agents named according to INCI: Aminotrimethylene, Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Am inotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Penta
  • Preferred complexing agents include organic phosphonates, alkanehydroxyphosphonates and carboxylates, which are available under the DEQUEST brand name from Thermphos.
  • a particularly preferred complexing agent is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid), which is sold, for example, as Dequest 2010.
  • Dequest® 2066 diethylenetriaminepenta(methylenephosphonic acid) or heptasodium-DTPMP is likewise suitable but less preferred since it gives worse cleaning outcomes.
  • the proportion of component Z3) if it is not 0%, is preferably from 0.001% to 10% by weight, more preferably from 0.005% to 7% by weight and especially preferably from 0.01% to 5% by weight, based in each case on the total weight of the laundry detergent composition of the invention.
  • the laundry detergent composition of the invention may also comprise one or more nonaqueous solvents or hydrotropes as component Z4).
  • a hydrotrope is a solvent which is neither water nor a conventional surfactant and promotes the solubilization of the surfactants and other components, especially polymer and complexing agent, in the liquid, in order to make it isotropic.
  • Suitable hydrotropes preferably include: monopropylene glycol (MPG), glycerol, sodium cumenesulfonate, ethanol, other glycols, e.g. dipropylene glycol, diethers and urea.
  • MPG monopropylene glycol
  • glycerol sodium cumenesulfonate
  • ethanol other glycols
  • other glycols e.g. dipropylene glycol, diethers and urea.
  • Preferred hydrotropes are MPG and glycerol.
  • the proportion of component Z4) if it is not 0%, is preferably from 0.001% to 50% by weight, more preferably from 0.01% to 30% by weight and especially preferably from 0.1% to 20% by weight, based in each case on the total weight of the laundry detergent composition of the invention.
  • the laundry detergent compositions of the invention may comprise one or more optional ingredients Z5), for example conventional ingredients which are typically used in laundry detergent compositions, especially textile laundry detergent compositions.
  • optional ingredients include viscosity regulators, bleaches, bleach-active compounds, bleach activators, bleach catalysts, photochemical bleaches, dye transfer inhibitors, dye fixatives, graying inhibitors, dispersants, fabric softeners, antistats, optical brighteners, enzymes, enzyme stabilizers, foam regulators, defoamers, deodorants, preservatives, disinfectants, fiber glidants, anticrease agents, buffer substances, fragrances, processing auxiliaries, colorants, dyes, pigments, corrosion inhibitors, fillers, stabilizers and other conventional ingredients of laundry detergent compositions.
  • the laundry detergent compositions of the invention may comprise further polymers to promote the washing performance.
  • polyalkoxylated polyethyleneimines e.g. polyethoxylated polyethyleneimines (EPEI)
  • EPEI polyethoxylated polyethyleneimines
  • polyester-based soil release polymers polymers that are used to promote the washing performance.
  • Polyethyleneimines are substances formed from ethyleneimine units —CH 2 CH 2 NH—, where the hydrogen on the nitrogen in the case of branching is replaced by a further chain of ethyleneimine units.
  • These polyethyleneimines can be prepared, for example, by polymerization of ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like. Specific methods of preparing these main polyamine chains can be found in U.S. Pat. Nos. 2,182,306, 3,033,746, 2,208,095, 2,806,839 and 2,553,696.
  • the proportion of the polyalkoxylated polyethyleneimines, if it is not 0%, is preferably from 0.05% to 10% by weight and more preferably from 0.1% to 6% by weight, based in each case on the total weight of the laundry detergent composition of the invention.
  • Polyester-based soil release polymers generally comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers that additionally contain polyalkylene glycols).
  • the polymeric soil release agents usable here especially include those soil release agents having (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments having a polymerization level of at least 2 or (ii) oxypropylene or polyoxypropylene segments having a polymerization level of 2 to 10, where the hydrophilic segment does not include any oxypropylene units, except when they are bonded via ether bonds to adjacent moieties at each end, or (iii) a mixture of oxyalkylene units comprising oxyethylene units and 1 to about 30 oxypropylene units, where the mixture contains a sufficiently great amount of oxyethylene units for the hydrophilic component to be hydrophilic enough to increase the hydrophilicity of conventional synthetic polyester fiber surfaces on deposition of the soil release agent on such a surface, where the hydrophilic segments contain
  • the polyoxyethylene segments of (a) (i) have a polymerization level of about 1 to about 200, although it is also possible to use higher levels, preferably of 3 to about 150 and more preferably of 6 to about 100.
  • a preferred polymeric soil release agent is a polyester having repeat units formed from alkylene terephthalate units, containing 10%-30% by weight of alkylene terephthalate units together with 90%-70% by weight of polyoxyethylene terephthalate units which derive from a polyoxyethylene glycol having a mean molecular weight of 300-8000.
  • this polymer examples are the commercially available substances TexCare® SRN170 and TexCare® SRN260 from Clariant. See also U.S. Pat. No. 4,702,857.
  • the proportion of the polyester-based soil release polymers if it is not 0%, is preferably from 0.05% to 5% by weight and more preferably from 0.1% to 3% by weight, based in each case on the total weight of the laundry detergent composition of the invention.
  • the laundry detergent compositions of the invention may comprise other polymer materials, for example dye transfer-inhibiting polymers or graying-inhibiting polymers.
  • the liquid laundry detergent compositions of the invention may comprise a polymer of polyethylene glycol and vinyl acetate, for example the lightly grafted copolymers according to WO 2007/138054.
  • amphiphilic graft polymers based on water-soluble polyalkylene oxides as graft base and side chains formed by polymerization of a vinyl ester component are capable of enabling a reduction in the surfactant contents with retention of high levels of removal of oily stains.
  • buffer substance preference is also given to using a buffer substance as well.
  • agents that are optionally used for production of anionic surfactants for example from LAS or fatty acids
  • buffer substances for regulation of pH is preferred.
  • Useful buffer substances include one or more ethanolamines, e.g. monoethanolamine (MEA) or triethanolamine (TEA).
  • MEA monoethanolamine
  • TEA triethanolamine
  • Other suitable amino alcohol buffer substances may be selected from the group consisting of compounds having a molecular weight of more than 61 g/mol, which includes MEA.
  • Possible alternatives to aminoethanol buffers are alkali metal hydroxides such as sodium hydroxide or potassium hydroxide.
  • the proportion of the buffer substances is preferably from 0.01% to 10% by weight and more preferably from 0.1% to 8% by weight, based in each case on the total weight of the laundry detergent composition of the invention.
  • the laundry detergent compositions of the invention may comprise one or more enzymes.
  • the one or more enzymes are selected from the group consisting of protease, mannanase, pectate lyase, cutinase, esterase, lipase, amylase and cellulase. Less preferred additional enzymes may be selected from peroxidase and oxidase.
  • the enzymes are preferably present together with appropriate enzyme stabilizers.
  • the proportion of the enzymes if it is not 0%, is preferably from 0.01% to 8% by weight and more preferably from 0.1% to 5% by weight, based in each case on the total weight of the laundry detergent composition of the invention.
  • the laundry detergent compositions of the invention may additionally comprise foam-boosting agents, polyelectrolytes, antishrink agents, anticrease agents, antioxidants, sunscreens, anticorrosives, antistats and ironing aids.
  • Liquid laundry detergent compositions of the invention may also comprise viscosity modifiers, pearlescent agents and/or opacifiers or other substances that cause visual effects.
  • the laundry detergent composition of the invention is liquid, the amount of water in the liquid laundry detergent composition of the invention may be from 1% to 95% by weight, based on the total weight of the liquid laundry detergent composition of the invention. Compositions having a very low water content are the most suitable for water-soluble portion pouches and capsules. In the case of pulverulent laundry detergent compositions of the invention, the amount of water is preferably less than 10% by weight, based on the total weight of the pulverulent laundry detergent composition of the invention.
  • the laundry detergent compositions of the invention optionally also comprise builders as component Z7).
  • Builders include inorganic and/or organic builders, in order to lower the hardness level of the water. They may be present in the laundry detergent compositions with proportions by weight of about 5% to about 80%.
  • Inorganic complexing agents include, for example, alkali metal, ammonium and alkanolammonium salts of polyphosphates, for instance tripolyphosphates, pyrophosphates and glass-like polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.
  • silicate builders are the alkali metal silicates, especially those with an SiO 2 :Na 2 O ratio between 1.6:1 and 3.2:1, and sheet silicates, for example sodium sheet silicates, as described in U.S. Pat. No. 4,664,839.
  • Aluminosilicate builders are particularly preferred for the present invention. These are especially zeolites having the formula Na z [(AlO 2 ) z (SiO 2 ) y ].xH 2 O in which z and y are integers of at least 6, the ratio of z to y is between 1.0 and about 0.5, and x is an integer from about 15 to about 264.
  • Suitable aluminosilicate-based ion exchangers are commercially available.
  • aluminosilicates may be of crystalline or amorphous structure, and may be naturally occurring or else synthetically produced.
  • Processes for the production of aluminosilicate-based ion exchangers are described in U.S. Pat. Nos. 3,985,669 and 4,605,509.
  • Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the zeolite A, zeolite P(B) (including those disclosed in EP-A-0 384 070) and zeolite X name. Preference is given to aluminosilicates having a particle diameter between 0.1 and 10 ⁇ m.
  • Suitable organic builders include polycarboxyl compounds, for example ether polycarboxylates and oxydisuccinates, as described, for example, in U.S. Pat. Nos. 3,128,287 and 3,635,830. Reference may likewise be made to “TMS/TDS” builders from U.S. Pat. No. 4,663,071.
  • Suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali metal, ammonium and substituted ammonium salts of polyacetic acids, for example ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and the soluble salts thereof.
  • polyacetic acids for example ethylenediaminetetraacetic acid and nitrilotriacetic acid
  • polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1
  • Citrate-based builders e.g. citric acid and the soluble salts thereof, especially the sodium salt, are preferred polycarboxylic acid builders which can also be used in granulated formulations, especially together with zeolites and/or sheet silicates.
  • phosphorus-based builders can be used, and especially when soap bars for washing by hand are to be formulated, it is possible to use various alkali metal phosphates, for instance sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate. It is likewise possible to use phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates as disclosed, for example, in U.S. Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137.
  • the proportion of component Z7) is preferably from 0.1% to 95% by weight, more preferably from 0.5% to 90% by weight and especially preferably from 0.5% to 80% by weight, based in each case on the total weight of the laundry detergent composition of the invention.
  • the laundry detergent compositions of the invention are in liquid form with a pH of 6 to 14, preferably from 6 to 12 and more preferably from 7 to 12.
  • the laundry detergent compositions of the invention comprise the one or more copolymers of component Z1) in an amount of 0.0005% to 10.0% by weight, more preferably in an amount of 0.001% to 5.0% by weight and especially preferably in an amount of 0.1% to 2.0% by weight, based in each case on the total weight of the laundry detergent composition of the invention.
  • the laundry detergent compositions of the invention comprise the one or more surfactants of component Z2) in an amount of 0.1% to 60.0% by weight, preferably in an amount of 0.5% to 50% by weight, more preferably in an amount of 1% to 45% by weight and especially preferably in an amount of 2% to 40% by weight, based in each case on the total weight of the laundry detergent composition of the invention.
  • the laundry detergent compositions of the invention contain from 0.0005% to 10.0% by weight of component Z1) and from 0.1% to 60.0% by weight of component Z2), based in each case on the total weight of the laundry detergent composition of the invention.
  • the laundry detergent compositions of the invention or the one or more copolymers of component Z1) are advantageously suitable for cleaning of textiles and preferably for cleaning of cotton-containing textiles.
  • the invention therefore further provides for the use of the laundry detergent compositions of the invention or of the one or more copolymers of component Z1) of the laundry detergent compositions of the invention for cleaning of textiles and preferably for cleaning of cotton-containing textiles.
  • the laundry detergent compositions of the invention or the one or more copolymers of component Z1) of the laundry detergent compositions of the invention are additionally advantageously suitable for reducing the resoiling of the textiles and preferably the resoiling of cotton-containing textiles on which the laundry detergent compositions of the invention or the one or more copolymers of component Z1) of the laundry detergent compositions of the invention have been employed.
  • the invention therefore further provides for the use of the laundry detergent compositions of the invention or of one or more copolymers of component Z1) of the laundry detergent compositions of the invention, preferably in a laundry detergent composition of the invention, for reducing the resoiling of the textiles and preferably the resoiling of cotton-containing textiles on which the laundry detergent compositions of the invention or the one or more copolymers of component Z1) of the laundry detergent compositions of the invention have been employed.
  • laundry detergent compositions of the invention comprise:
  • AAPTAC [3-(acryloylamino)propyl]trimethylammonium chloride (75% by weight active in aqueous solution)
  • MAPTAC [3-(methacryloylamino)propyl]trimethylammonium chloride (50% by weight active in aqueous solution)
  • MESNA sodium 2-mercaptoethanesulfonate (100% active)
  • NIPAM N-isopropylacrylamide (100% active)
  • the aqueous solution is purged with nitrogen for 30 minutes and heated to 60° C.
  • the amount of initiator specified in table 1 (VA-44) is dissolved in 10 g of distilled water and metered in over a period of 90 minutes.
  • stirring is continued at an internal temperature of 60° C. for a further hour.
  • the conversion of the reaction is checked by a subsequent analysis of the solids, and any unconverted monomers, if necessary, are reacted via a small addition of a 10% by weight aqueous solution of the initiator already used beforehand until full conversion has been attained. Thereafter, the reaction mixture is cooled down to room temperature (20-23° C.).
  • Table 1 lists synthesis examples for copolymers of component Z1) of the laundry detergent compositions of the invention.
  • the test fabric used was white standard cotton specimens (WFK 10A, from WFK Testgewebe GmbH). The fabrics were prewashed three times with the laundry detergent compositions. Then the specimens were rinsed, dried and stained with a sebum/carbon black mixture (5% by weight of carbon black). The stained specimens were left to dry for 24 hours, and then the color was measured according to the CIE-Lab scale using a MACH5 instrument (Color Consult, Holland) calibrated with a Datacolor 650 spectrophotometer. The specimens were then washed again with the same laundry detergent compositions as in the prewash step. After rinsing and drying of the washed specimens, another measurement of the color of the stain was conducted with the MACH5 instrument.

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US11530373B2 (en) 2016-11-28 2022-12-20 Clariant International Ltd Cleaning agent compositions containing copolymer
US11649310B2 (en) 2016-11-28 2023-05-16 Clariant International Ltd Copolymers and the use of same in cleaning agent compositions
US11692052B2 (en) 2016-11-28 2023-07-04 Clariant International Ltd Copolymers and use thereof in cleaning-agent compositions
US20200407494A1 (en) 2017-11-28 2020-12-31 Clariant International Ltd. Renewably Sourced Soil Release Polyesters
US11884775B2 (en) 2017-11-28 2024-01-30 Clariant International Ltd. Renewably sourced soil release polyesters
US11427787B2 (en) * 2018-12-20 2022-08-30 Ecolab Usa Inc. Surfactant blend for removal of fatty soils
CN117720969A (zh) * 2023-12-13 2024-03-19 广东欧蝶兰高新科技日用品有限公司 一种运动衣物洗涤使用的洗衣液及其制备方法

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JP2020513443A (ja) 2020-05-14
DE102016223584A1 (de) 2018-05-30
CN110088259A (zh) 2019-08-02
WO2018095923A1 (de) 2018-05-31

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